Sciencemadness Discussion Board

Alternative to Nitric acid /research

plante1999 - 16-5-2011 at 08:30

Many time i wanted to disolve metals like copper , nickel without very high suscess because i dont have nitric acid , and nitrate salt is not disponible to me. So , I desided to find an cheap alternative , altoug i need to make more work to get an high yield product. Many of us probably want an oxidizer that have no Metals ion so here is my first (and l1 month research) to get this and this yield i will separate this raport in 4 part , but before this i will mention that this topic is for improuvement , not only of this compound , but alls others alternatives.The compound that I talk about is HOCl , befor posting please read all the report.



Warning!

This compound schould not mixed with : nitrogen compound and HCl this compound is very corrosive to human tissu and at high consentration can make fire with organic.
If you arrent experienced with oxidizer , dont do this. NEVER mix it with something that you dont know the product of reaction.

Precaussion for improuvement:
when you synthesis make sure that NO chloride salt is present , So dont think using Calcium Hypochlorite instaid , ive ear that Lithium hypochlorite could substitute the Sodium hypochlorite , this could be an improuvement

Reagent:
10% NaOCl Pool industry grade
H2SO4 98% ACS Reagent
H2O Distiled
CHCl3 Triple distilled
Experimental

Take 14.9g of 10% NaOCl and ad it to and Round Bottom Boiling Flask .Instal an bubler trough 5ml of CHCl3 in a test tube , witch will be cooled in HCl snow mixture to The Trichloromethane layer ad 4 g of distilld water. Ad to the RBF 12g of H2SO4 (the real molar ratio is 0.98g but it need more tho hydrolise the HOCl). After 5min of seting heat the mixture(keep the temperature to 50-65 degree C) , stop when white fume evolve.

This is suposed to hapen:
2NaOCL + H2SO4 -) Na2SO4 + 2HOCl
but with ot temp the H2SO4 hydrolise the HOCl:
2HOCl-) H2O + Cl2O
the Cl2O is a gas , it will disolve in the 5ml of distill water to make HOCl , some peaple will probably think that it will disproportionnate to Cl2 , but this appen just in the presense of Cloride ion.

This also appen:
2CHCl3 + Cl2O -) 2CCl4 + H2O



You will get about 15ml of 5-6% HOCl.

futur improuvement and note: better source of hypochlorite ion , better setup , better cooling.H2SO4 can be substitued with H3PO4 Or citric acid , the last one being the best but i have only 25g of it.

the mode of opperation of the acid is this:

2HOCl + 2Cu -) CuCl2 + CuO + H2O

Other interessing compound :
Peracetic acid


thanks!!

[Edited on 16-5-2011 by plante1999]

[Edited on 17-5-2011 by plante1999]

[Edited on 17-5-2011 by plante1999]

ScienceSquirrel - 16-5-2011 at 09:29

Have you considered using 30% hydrogen peroxide in the presence of an acid?
It is a very powerful oxidising agent and the only byproducts are water and some oxygen from self decomposition.

AndersHoveland - 16-5-2011 at 13:14

I have noticed that 30% concentrated H2O2 with 30% concentrated HCl solution is able to rapidly attack and dissolve copper.

bbartlog - 16-5-2011 at 16:18

HCl plus bubbled air (e.g. through an aquarium airstone via a pump) also works. Slowly (takes days)... but air is free. Main problem is that this method can put a lot of HCl in the air if you don't have some sort of scrubbing or suitable exhaust set up.

plante1999 - 16-5-2011 at 16:29

Yes ive consider the two proposition , but the max hydrogen peroxide conssentration is 3% witch i conssentre to 15% by selective freezing , but like i said no high yield reaction is obtained , i dont even talk of air + HCl , with the 5% sol i made i can get very high yield in short ammont of time.

[Edited on 17-5-2011 by plante1999]

[Edited on 17-5-2011 by plante1999]

[Edited on 17-5-2011 by plante1999]

m1tanker78 - 16-5-2011 at 16:38

I exclusively use 3% H2O2 + concentrated HCl to etch printed circuit boards (copper cladding). The combination works ~ 3-5x faster than FeCl3 for the same purpose and far less cost. Poor man's nitric... :P

Tank

S.C. Wack - 16-5-2011 at 16:41

There are alternatives in making HOCl, in threads with hypochlorous acid in the title. Calcium hypochlorite can be used.

plante1999 - 16-5-2011 at 16:43

I dont think so , the chloride ion will react with hypochloride to get chlorine gas. this could be a very good way to make incontroled synthesis.

HCl + HOCl -) H2O + Cl2

edit :
you could do it but potantial harmfull gas will be produce.

[Edited on 17-5-2011 by plante1999]

[Edited on 17-5-2011 by plante1999]

hyperkinetic - 16-5-2011 at 17:20

Bleach and Hydrochloric acid is a nasty but effective metal dissolving mixture, it does fume Chlorine and Chlorine oxides and death.

Sodium or potassium nitrate dissolved in Hydrochloric acts like Aqua Regia to some extent, dissolves much and fumes a lot just like Aqua Regia.

I've heard bubbling Ozone into Hydrochloric is very effective, acting like peroxide and HCl. I've never had a chance to try it.

You can still get dilute nitric as pH down in hydroponic supply stores. I've used the dilute stuff to coax carbon-less stainless steel into dissolving in HCl with great success.

You should be able to find it in Quebec. You can also pick out the grains of sodium nitrate from Drano, if you have the time...

S.C. Wack - 16-5-2011 at 17:26

Usually I would suggest writing to the editor, but sending corrections to an article from 1912, in a journal that no longer exists, would be pointless.

It was slightly weird how the lead authors obit looked at just now (in J. Chem. Soc., 1926, 993-1050) was immediately followed by the obit for the familiar name Sir TE Thorpe.

PHILOU Zrealone - 17-5-2011 at 03:47

You can also use NH4OH and air...so copper wire unperfectly immersed in NH4OH will dissolve its oxyde layer in a deep blue ammoniacal solution...the naked metallic copper will readily oxydise again and further dissolve.

I have made the experiment with Eurocents (Iron steel plated with Cu) into a 500ml Coca Cola PET bottle with screewed cap.
The bottle was shaked from time to time during a few weeks and the bottle was under gas depression...so I let from time to time fresh air come inside the bottle by unscreewing the cap.
In conclusion:
CuO + NH4OH --> Cu(NH3)4(OH)2
Cu + O2 + H2O --> CuO + Cu(OH)2
or in short:
Cu + 1/2O2 --> Cu(2+) + O(2-)
At the end of the process all the copper was dissolved leaving silvery iron steel coin core!

The same kind of experiment can be done with vinegar or acetic acid and air...
Note the fact the reaction works best at the interface between the wet solid metal and the air, do not immerse completely the metal into the fluid, it would work much slower.

The process works because the oxyde layer is dissolve as soluble acetate or ammonia complex and metal is subjected to air oxydation under wet conditions.

I suppose it could work with H2O2 instead of fresh air.




[Edited on 17-5-2011 by PHILOU Zrealone]

plante1999 - 17-5-2011 at 08:35

I made a rapid guide for who want to use 65% Ca(OCl)2 from Pool shock, ive tested it and work great , make sure that you made the last part!


Synthesis of 40% HOCl sol.

Warning:
same as up there but now : This reaction should be done outside Chlorine gas is produce.

Reagent:
65% Ca(OCl)2 pool industry grade
98% H2SO4 ACS Reagent
H2O Distilled

Experimental:
Disolve 16.6g of H2SO4 in 8ml of water.
Take 22g of 65% Ca(OCl)2 and ad it to an 50ml beaker.
Ad the sulfuric acid to the beaker and go away,lets react for 20 minute.
Lets it sit for 12 hour , than take a glass pipet and take slowly the HOCl sol. layer , store it in amber vials.

I will ad the equation for the reaction later.

picture in 8 hour and final guide in 24.

[Edited on 17-5-2011 by plante1999]

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DJF90 - 17-5-2011 at 09:51

I somehow doubt that a 40% solution of HOCl is going to be stable enough to sit around for 12 hours. There would surely be some decomposition.

AJKOER - 17-5-2011 at 10:26

Hi:

I use HClO to dissolve Iron (Fe) to create a brownish red solution of FeCl3 (even dilute HClO works, see preparation below).

How to Make Dilute HClO Inexpensively:

1. Add Vinegar to Bleach (NaClO) and heat to drive off mostly Cl2O, chlorine monoxide the anhydride of HClO.

2. Use Seltzer water (H2CO3) to NaClO in place of acetic acid. Wait for at least a day, and proceed as above. The chemistry is:

NaClO + H2CO3 = NaHCO3 + HClO

3. Dissolve Cl2O in water:

Cl2O + H2O = 2HClO

where Cl2O is reputedly created by passing Cl2 into KOH. Note, I have not attempted this method which is mentioned in some earlier chemistry text.

Note, only dilute solutions of HClO are stable. HClO readily decomposes especially if concentrated with the dominant reaction as follows:

3 HClO = HClO3 + 3 HCl

This is an important point as you may be producing some chlorates unknowingly. Solutions and the dry salt of Ammonium Chlorate (and heavy metals), for example, should be particularly avoided given there, at times, sensitive and highly explosive behavior.

To are lesser degree, pure HClO will decompose as follows:

2 HClO = 2 HCl + O2

however, in the presence for example of H2O2, CuO, CoO and organic material, the release of O2 is accelerated. Also, in the presence of HCl, there is an equilibrium reaction producing chlorine water:

HCl + HClO <==> H2O + Cl2

Heat and light are know to increase the rate of HClO decomposition for both reactions noted.

plante1999 - 17-5-2011 at 10:31

40% sol decompose sommewath but it seem that it is around 30-45%. at this time it seem stable.



[Edited on 17-5-2011 by plante1999]

Neil - 17-5-2011 at 10:32

Quote: Originally posted by S.C. Wack  
Usually I would suggest writing to the editor, but sending corrections to an article from 1912, in a journal that no longer exists, would be pointless.

It was slightly weird how the lead authors obit looked at just now (in J. Chem. Soc., 1926, 993-1050) was immediately followed by the obit for the familiar name Sir TE Thorpe.



I've re-read this thread several times but I still have no idea what you were referring too :(


@plante you may want to check out the stability data in this thread.





S.C. Wack - 17-5-2011 at 13:13

Quote: Originally posted by Neil  
I've re-read this thread several times but I still have no idea what you were referring too :(


Note how the post immediately above my last post was posted 6 minutes earlier. I was responding to the post before that, which was a response to me. Thorpe was the editor of an encyclopedia that used to be read and referred to by some of the membership here.

[Edited on 17-5-2011 by S.C. Wack]

decomposition hypochlorous acid

AndersHoveland - 17-5-2011 at 13:37

Quote: Originally posted by m1tanker78  
I exclusively use 3% H2O2 + concentrated HCl to etch copper The combination works faster than FeCl3 for the same purpose.


I have calculated from a table of reduction potentials that FeCl3 would react with elemental silver (the formation of AgCl is very favorable and alters the potentials). Since the AgCl that should form is insoluble, however, only the thin surface layer of the metal would be expected to react. Perhaps someone would like to try FeCl3 with NH4OH to see if that can dissolve silver.

Also, to respond to AJKOER,
I think your formula is incorrect:
3 HClO = HClO3 + 3 HCl

I think the correct equation is:
(8)HOCl --> (4)H2O + (2)ClO2 + (3)Cl2

Of course in alkaline solution, if the hypochlorite is sufficiently concentrated, the formula which you described is true:
(3)OCl- --> ClO3- + (2)Cl-

[Edited on 17-5-2011 by AndersHoveland]

UnintentionalChaos - 17-5-2011 at 13:41

Quote: Originally posted by AndersHoveland  
Quote: Originally posted by m1tanker78  
I exclusively use 3% H2O2 + concentrated HCl to etch copper The combination works faster than FeCl3 for the same purpose.
Tank


I have calculated from a table of reduction potentials that FeCl3 would react with elemental silver (the formation of AgCl is very favorable and alters the potentials). Since the AgCl that should form is insoluble, however, only the thin surface layer of the metal would be expected to react. Perhaps someone would like to try FeCl3 with NH4OH to see if that can dissolve silver.


That would make hydrated Fe2O3.

AndersHoveland - 17-5-2011 at 13:51

The reaction which was meant is:
Ag + Fe[+3] + Cl[-] --> AgCl + Fe[+2]

Of course ferric nitrate would not be expected to react with silver, only ferric chloride.

I would think that dipping silver into a solution of ferric iodide would cause the surface of the metal to turn yellow; there probably would not be any obvious reaction in FeCl3.

[Edited on 17-5-2011 by AndersHoveland]

plante1999 - 17-5-2011 at 16:29

Now ive checked my 40% and an very huge mess have been made from the beaker , very bas smell is comming from it , dont do the guide up there , i will uptate it to get only 15% and i will use citric acid in place of the sulfuric acid.

[Edited on 18-5-2011 by plante1999]

plante1999 - 17-5-2011 at 17:41

Good news! ive made an good synthsis with citric and 15% sol , here some random picture , the rapport will be tommorow. In the begining i wanted to use oxalic acid because i can get it cheaply at the pharmacy but i reavised when i see its a dengerous toxic substance (calcium oxalate) so i decided to use a large part of my citric acid reagent , but i think the best choise is making calcium citrate , it is a food aditive , not an toxic compound....






Many picture is missing but i dont want to show all of them befor i make my report....

Edit : Fail i dont wear my nitril glove..... I was to happy and i forgot it , I am ashamed....

[Edited on 18-5-2011 by plante1999]

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AndersHoveland - 17-5-2011 at 21:37

That label is amusing: "Ca(OCl)2 + impurities ".

Just what exactly are those pesky impurities in store bought bleaching powder? In terms of a clean reaction, it leaves much to be desired...

I find that the crude bleaching powder bought in stores leaves much undesirable material in my reactions. This is one of those chemicals which, while being obtainable "off the self", is better prepared by oneself.



[Edited on 18-5-2011 by AndersHoveland]

plante1999 - 18-5-2011 at 03:28

Quote: Originally posted by AndersHoveland  
That label is amusing: "Ca(OCl)2 + impurities ".

Just what exactly are those pesky impurities in store bought bleaching powder? In terms of a clean reaction, it leaves much to be desired...

I find that the crude bleaching powder bought in stores leaves much undesirable material in my reactions. This is one of those chemicals which, while being obtainable "off the self", is better prepared by oneself.



[Edited on 18-5-2011 by AndersHoveland]


Its is the same stuf as you buy in the pool store (65%) I dont think you can do better purity than 75%.

anyway , ive checked my sol. and..... it is frost , the next time i will re try in an hot place ..... hum ..... in about 12 hour again....

bbartlog - 18-5-2011 at 04:33

Quote:
a dangerous toxic substance (calcium oxalate)


If you eat it or rub it on your skin, sure. But frankly almost every other compound you're working with (H2SO4, HOCl, Ca(OCl)2, to say nothing of Cl2O) is more dangerous.

plante1999 - 18-5-2011 at 08:10

The beaker tath have frosted is now like a beaker with plaster in....
''If you eat it or rub it on your skin, sure. But frankly almost every other compound you're working with (H2SO4, HOCl, Ca(OCl)2, to say nothing of Cl2O) is more dangerous.''
Ok ok i understan , i will try with oxalic....
''That label is amusing: "Ca(OCl)2 + impurities ".
yes i think it is funny but it is honnest that they wrigth it....

Today i will try to disolve all of the reactan and i will try with oxalic an citric acid to make 10% sol , if it work i will make more concentred sol.


[Edited on 18-5-2011 by plante1999]

plante1999 - 18-5-2011 at 08:39

Sorry for the double post.

I think that HClO3 can also be an good substitute for nitric , i already made it at arround 15% sol with very high yield. I will remade chlorate and after i will post picture and synthesis , this synthesis is prety cool to do altough it is only a routine synthesis.

short of the report i will made:
disolve 0.9g of Oxalic acid in 10ml H2O a beaker.
disolve 2.45g of KClO3 in 10 ml of HOT H2O.
ad the first sol to the second.
lets sit 12 hour and take a pipet to get the 15% sol in an amber vial.

in one month at 10 degree Celcius no visible decomposition is occured.

plante1999 - 18-5-2011 at 14:42

Now after multiple test i can said that it is almost impossible to use Calcium hypochlorite as source of hypochlorite ion. i am making chlorate at this time (calcium hypochlorite decomposition) to make an report for HClO3.

Neil - 18-5-2011 at 15:10

Plante, Why not rely on the reaction products being formed just before the addition of the metal you wish to dissolve?

Many maybe most of the solutions used to dissolve PGM and related metals, decompose and do not have great storage life.

If your goal is to create a cheap alternative to nitric, it seems you already have what you are after.

Rather then trying to make a somewhat stable solution of a dangerous substance, why not keep the very stable and slightly safer ingredients separated and only mix them up immediately before they are needed?

On a side note, have you tested these solutions on a metal yet?

plante1999 - 18-5-2011 at 15:24

I have tested 5% sol of HOCl (made with NaOCl) on copper and it work.
ive also tested HClO3 15% on copper and it work briantly , at this time i am waiting for my chlorate to be finish so i can make an report for synthesis of 30% sol.

''Plante, Why not rely on the reaction products being formed just before the addition of the metal you wish to dissolve?''

because all acid need to be purified , at this Time HClO3 seam to be te best , but if i found solid lithium hypochlorite i will re-try HOCl , but at 25-30%

does anyone have worked with paracetic acid?

[Edited on 18-5-2011 by plante1999]

AJKOER - 18-5-2011 at 20:46

With respect to Copper in a NH4OH solution. I have a observed a slightly different reaction when using air versus a closed chamber with NH4OH/H2O2 and copper. One would expect using a O2 rich environment to be more efficient, but not observed.

My guess is that the reaction is not moving forward as expected because the active catalyst is perhaps CO2 (or something else, like bacteria), present in the air that gets dissolved into the solution. The formation of a copper carbonate complex (or nitrite from bacterial oxidation of the NH3), my personal speculation, may be involved in moving the reaction!

AJKOER - 18-5-2011 at 20:49

With respect to Copper in a NH4OH solution. I have a observed a slightly different reaction when using air versus a closed chamber with NH4OH/H2O2 and copper. One would expect using a O2 rich environment to be more efficient, but not observed.

My guess is that the reaction is not moving forward as expected because the active catalyst is perhaps CO2 (or something else, like bacteria), present in the air that gets dissolved into the solution. The formation of a copper carbonate complex (or nitrite from bacterial oxidation of the NH3), my personal speculation, may be involved in moving the reaction!

Neil - 18-5-2011 at 21:04

If you find a bacterial that can survive in three powerfull anti bacterial agents all mixed together, You should certainly bring it to someones attention.

Doesn't H2O2 break down ammonia? if your solution with H2O2 and ammonia went slower, it seems plausible that it was because you were destroying the ammonia.

AJKOER - 19-5-2011 at 06:32

I just came across one of my notes, which I believe came from a Google online book that dealt with mining metals. The note was that CuO dissolves in NH4OH in the presence of a few drops of acid or ammonium carbonate! This is apparently performed on a big scale to recover copper.

As such, it may be the CO2 in air that reacts with NH4OH forming some ammonium carbonate that is the catalysis for the reaction to dissolve the copper which has been oxidized by O2.

Now, as to why it is best to have the copper half out of the solution, I would guess that the copper wire serves as a condensation point for dew. These drops of dew are, in effect, mini-drops of H2CO3, or anything else that is in your local acid rain. The copper wire then directs the acid directly into the solution, only in small quantities of course, but enough to be the reaction catalyst.

If I am correct, a solution of NH3, H2O2 and a little carbonated water in a close vessel (periodically refreshed) should more quickly dissolve the copper.

AJKOER - 19-5-2011 at 10:14

OK, two points.

1. You cannot (and do not need) a strong mineral acid (like H2SO4) to add to Ca(OCl)2 if it is derived from bleaching powder where the "impurities" might include CaCl2. xH2O (a Calcium Chloride Hydrate). Why? Adding H2SO4 to CaCl2 creates HCl:

CaCl2 + H2SO4 = CaSO4 + 2 HCl

As the HCl reacts with the created HClO from:

Ca(OCl)2 + H2SO4 = 2 HClO + CaSO4

to liberate Chlorine from the breakdown of HClO with HCl:

HCl + HClO = Cl2 + H2O

A weak acid is preferred since even in the presence of a chloride, no HCl will be created and hence, no Cl2 liberated!

2. HClO dissolves Copper and produces an oxy-chloride, 3 Cu(OH)2.CuCl2 (and not just CuCl2 as you might expect. Note, similar oxy-chlorides and even oxy-nitrates are seen with Lead). Copper(II) oxygen chloride is quoted as being one of the most importance copper salts in the industry (in fungicides, adhesive & dispersive agents and fillers per the "Concise Encyclopedia of Chemistry" by DeGruyter).

6 Cu +6 HClO = 3 Cu(OH)2.CuCl2

plante1999 - 19-5-2011 at 16:06

Does you think i dont have think to this ? I have calutated the molar mass of my reactan an product in fonction of 65%Calcium hypochlorite and 25 CaCl2.

For the last par you probably have reason.

My chlorate will be finished tommorow.....

Where i can get lithium hypochlorite (pur) or lithium compound ? OTC please.

[Edited on 20-5-2011 by plante1999]

[Edited on 20-5-2011 by plante1999]

[Edited on 20-5-2011 by plante1999]

Neil - 19-5-2011 at 18:56

iodine/bromine free pool sterilizing supplies.

plante1999 - 15-8-2011 at 04:41

Here the first par for a substitute to nitric acid , a second part will be made for pur bromic acid , like many of my video there is many mistake.

<iframe sandbox width="560" height="349" src="http://www.youtube.com/embed/XlCPh17rVFc" frameborder="0" allowfullscreen></iframe>

[Edited on 15-8-2011 by plante1999]

[Edited on 15-8-2011 by plante1999]